The paper analyzes the entropy of a system composed by non-interacting and indistinguishable particles whose quantum state numbers are modelled as independent and identically distributed classical random variables. The crucial observation is that, under this assumption, whichever is the number of particles that constitute the system, the occupancy numbers of system's quantum (micro)states are multinomially distributed. This observation leads to an entropy formula for the physical system, which is nothing else than the entropy formula of the multinomial distribution, for which we claim novelty, in the sense that it is proposed here for the first time that the entropy of the multinomial distribution is the entropy of the physical system. The entropy formula of the multinomial distribution unveils yet unexplored connections between information theory and statistical mechanics, among which we mention the connection between conditional entropy of the random microstate given the random occupancy numbers and the Boltzmann-Planck entropy $\log(W)$ and between these two and the Gibbs correction term $\log(N!)$, thermalization and communication-theoretic preparation of a thermal state, accessible information of the thermal state and physical entropy of the thermalized system. A noticeable specific result that descends from our approach is the exact quantum correction to the textbook Sackur-Tetrode formula for the entropy of an ideal gas at the thermal equilibrium in a container.
The paper analyzes the entropy of a system composed by non-interacting and indistinguishable particles whose quantum state numbers are modelled as independent and identically distributed classical random variables. The crucial observation is that, under this assumption, whichever is the number of particles that constitute the system, the occupancy numbers of system's quantum (micro)states are multinomially distributed. This observation leads to an entropy formula for the physical system, which is nothing else than the entropy formula of the multinomial distribution, for which we claim novelty, in the sense that it is proposed here for the first time that the entropy of the multinomial distribution is the entropy of the physical system. The entropy formula of the multinomial distribution unveils yet unexplored connections between information theory and statistical mechanics, among which we mention the connection between conditional entropy of the random microstate given the random occupancy numbers and the Boltzmann-Planck entropy log(W) and between these two and the Gibbs correction term log(N!), thermalization and communication-theoretic preparation of a thermal state, accessible information of the thermal state and physical entropy of the thermalized system. A noticeable specific result that descends from our approach is the exact quantum correction to the textbook Sackur-Tetrode formula for the entropy of an ideal gas at the thermal equilibrium in a container.
In this work, we compare three formulations of thermodynamic entropy for a non-interacting bosonic gas: (i) the grand-canonical Bose-Einstein entropy, (ii) the finite-N canonical entropy obtained from the exact partition function (Ziff, Uhlenbeck, and Kac construction), and (iii) the entropy of a multinomial distribution with Boltzmann categorical probabilities and temperature determined from Clausius' equation. It is well-known that the grand-canonical Bose-Einstein systematically overestimates entropy of canonical systems in regimes where particle-number fluctuations are significant. The exact canonical entropy correctly enforces the particle-number constraint, but recent experimental results suggest that it also overestimates particle-number fluctuations below the crossover temperature. The multinomial distribution is less common in thermodynamics. It addresses in a mathematically exact way the puzzle of the famous -log(N!) term introduced by Gibbs as a deus ex machina in discussions of thermodynamic entropy. One remarkable consequence is that the entropy of the multinomial distribution overcomes the issue of negative entropy at low temperature that affects the Gibbs and the Sackur-Tetrode entropies at low temperature. The analysis presented in the paper shows that the multinomial distribution, equipped with a categorical distribution calibrated in such a way that the resulting multinomial entropy fits Clausius' equation, provides accurate approximations to the canonical entropy in the classical regime, while it is smaller than the canonical entropy below the crossover temperature. One feature of the multinomial distribution is that it predicts lower peak variance of the number of particles in the ground state than the canonical distribution. This is in agreement with recent experimental results; hence, this paper identifies the thermodynamically calibrated multinomial distribution as a candidate alternative to the canonical distribution for thermodynamic bosonic entropy in finite systems.
Abstract The quantum thermodynamics of the ideal gas is treated by means of the particle entropies σ=ka. The non-dimensional entropy numbers a are calculated by the extended, temperature-dependent Schrödinger equation applying periodic boundary conditions. The Boltzmann constant k represents the atomic entropy unit. The quantized particle entropies a are used to calculate the Boltzmann distribution f=exp(α−a), the density of entropy levels D(a), the dimensionless chemical potential α=μ/kT, etc. – The thermodynamics of the ideal gas is treated on the basis of entropy quanta by means of the density matrix formalism. In this way we obtain the total particle entropy A, the thermodynamic entropy S (equation of Sackur-Tetrode), the internal and the Helmholtz free energy E and F, respectively, etc. Moreover, it can also be shown on the basis of entropy quanta that the entropy of a closed system in thermal equilibrium has a maximum value, S=S max. Against this, the entropy S ′ of an arbitrary non-equilibrium state is always smaller, S′ < S max (second law of thermodynamics). – Application of ordinary density matrix theory to a closed system of N particles leads to the result that the entropy S does not change in time, dS/dt=0, regardless whether we consider an equilibrium state, S=S max, or a non-equilibrium state, S=S′. Consequently, S cannot irreversibly change from S′ to S max. However, any irreversible process is accompanied by a positive entropy production P=dS/dt>0. In order to overcome this obvious contradiction, we discuss the entropy evolution in time by means of the commutator equation G =i[ P , t ], which is deduced from very general assumptions. Here P and t are the operators of the entropy production P and the time t. Accordingly, P and t do not commute in general, and hence P and t are not sharply defined simultaneously. Instead we have uncertainties ΔP and Δt, which are expressed by the uncertainty relation of the N-particle system, ΔPΔt≥(1/2)|〈 G 〉|=(γ/2)k. This P − t uncertainty relation easily allows a discussion of the evolution of the entropy S in time t from S′ to S max. Now the irreversible steps are correctly described by the entropy production P=dS/dt > 0, and the thermal equilibrium by P=0, ∆P=0, and thus the lifetime ∆t=∞.
The paper analyzes the probability distribution of the occupancy numbers and the entropy of a system at the equilibrium composed by an arbitrary number of non-interacting bosons. The probability distribution is obtained through two approaches: one involves tracing out the environment from a bosonic eigenstate of the combined environment and system of interest (the empirical approach), while the other involves tracing out the environment from the mixed state of the combined environment and system of interest (the Bayesian approach). In the thermodynamic limit, the two coincide and are equal to the multinomial distribution. Furthermore, the paper proposes to identify the physical entropy of the bosonic system with the Shannon entropy of the occupancy numbers, fixing certain contradictions that arise in the classical analysis of thermodynamic entropy. Finally, by leveraging an information-theoretic inequality between the entropy of the multinomial distribution and the entropy of the multivariate hypergeometric distribution, Bayesianism of information theory and empiricism of statistical mechanics are integrated into a common "infomechanical" framework.
As known, a method to introduce non-conventional statistics may be realized by modifying the number of possible combinations to put particles in a collection of single-particle states. In this paper, we assume that the weight factor of the possible configurations of a system of interacting particles can be obtained by generalizing opportunely the combinatorics, according to a certain analytical function f{π}(n) of the actual number of particles present in every energy level. Following this approach, the configurational Boltzmann entropy is revisited in a very general manner starting from a continuous deformation of the multinomial coefficients depending on a set of deformation parameters {π}. It is shown that, when f{π}(n) is related to the solutions of a simple linear difference-differential equation, the emerging entropy is a scaled version, in the occupational number representation, of the entropy of degree (κ,r) known, in the framework of the information theory, as Sharma-Taneja-Mittal entropic form.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.